The present invention relates to thermally and hydrolytically stable polyenaminonitriles, including those which can be cyclized and cured by heating. According to a preferred feature, the curing reaction proceeds without the evolution of volatile by-products which simplifies the fabrication of hole-free shaped solid masses such as thin films as well as essentially defect-free composites.
U.S. Pat. No. 4,148,844 to von Bonin et al. discloses the production of a heat curable resin by polymerizing a polycarbodiimide and vinyl monomer.
U.S. Pat. No. 4,421,920 to Baudouin et al. discloses a method for producing 4-amino-chloroquinolines.
British Patent Publication GB 2,103,227 A (1983) to Papir discloses the production of tractable, i.e. shapeable, polyquinolines in an m-cresol solution of phosphorus pentoxide as acidic catalyst from a precursor monomer, such as 5-acetyl-2-amino-benzophenone, which on heating yields poly 2,6-(4-phenylquinoline), recovered as a coagulated solid by contacting the resulting acidic reaction solution with a basic coagulation bath of an amine dissolved in a protonic solvent such as water or ethanol, e.g. an ethanol/triethylamine mixture.
The coagulated solid of Papir may be made into a tractable film by redissolving the polyquinoline in an m-cresol solution of phosphorus pentoxide with heating and pouring of the solution onto a heated surface, followed by quenching in an ethanol/triethylamine mixture and oven drying, thereby inherently liberating volatile by-products such as water or ethanol and producing pin-hole defects in the solid product. The film may be doped to change its electrical properties.
Clearly, in the Papir system, the m-cresol and phosphorus pentoxide comprise an acidic solvent which functions as a catalyst to effect loss of water as a volatile by-product.
None of these references discloses the production of polyenaminonitrile or the cyclization of this polymer into the corresponding poly(4-amino-quinoline) or other poly(aminoquinoline) through the use of heat or other means. The chemistry used in these references is also different from that used for the present invention.
The following articles are all instructive in understanding the present invention:
[1] Rappoport, Z., Adv. Phys. Org. Chem., 1969, 7, 1 PA0 [2] Modena, G., Acc. Chem. Res., 1971, 4, 73 PA0 [3] Rappoport, Z., Acc. Chem. Res., 1981, 14, 7 PA0 [4] Ueda, M.; Kino, K.; Hirone, T.; Imai, Y., J. Polym. Sci., Polym. Chem. Ed., 1976, 14, 931 PA0 [5] Imai, Y.; Ueda, M.; Otaira, K., J. Polym. Sci., Polym. Chem. Ed., 1977, 15, 1457 PA0 [6] Ueda, M; Otaira, K.; Imai, Y., J. Polym. Sci., Polym. Chem. Ed., 1978, 16, 2809 PA0 [7] Imai, Y.; Sakai, N.; Susaki, J.; Ueda, M., Makromol. Chem., 1979, 80, 1797 PA0 [8] Pavlisko, J. A.; Huang, S. J.; Benicewicz, B. C., J. Polym. Sci., Polym. Chem. Ed., 1982, 20, 3079 PA0 [9] Moore, J. A.; Kochanowski, J. E., Macromolecules, 1975, 8, 121 PA0 [10] Moore, J. A.; Mitchell, T. D., J. Polym. Sci., Polym. Chem. Ed., 1980, 18, 3029 PA0 [11] Moore, J. A.; Mitchell, T. D., J. Polym. Sci., Polym. Chem. Ed., 1983, 21, 1305 PA0 [12] Kimura, S., Makromol. Chem., 1968, 117, 203 PA0 [13] Bass, R. G.; Sinsky, M. S.; Connell, J. W.; Hergenrother, P. M., Polym. Prepr., 1984, 25 (2), 59 PA0 [14] Conrad, M.; Limpach, L., Chem. Ber., 1887, 20, 944 PA0 [15] Conrad, M.; Limpach, L., Chem. Ber., 1888, 21, 525 PA0 [16] Brown, R. F., "Pyrolytic Methods in Organic Chemistry", Academic Press, New York, 1980 PA0 [17] Libis, B.; Fleury, J. P., Bull. Soc. Chim. Fr., 1965, 3323 PA0 [18] Friedrich, K., Angew. Chem. Intl. Ed., 1973, 6, 959
References [1] through [3] disclose the mechanisms of a vinylic nucleophilic substitution. This reaction has been inaccurately referred to as a vinylogous nucleophilic substitution in articles [4] through [8], where other polymers have been produced in the same way.
.beta.-halo-dicyanovinyl compounds react with aromatic amines, in most cases by a two step addition-elimination mechanism to produce enaminodinitriles in high yield. See article [3]. .beta.-halo-monocyanovinyl compounds should also be effective.
Other researchers have produced poly(enamines) by condensation of bis-(.beta.-keto esters) with diamines (see articles [9] through [12]) and by Michael addition of aromatic diamines to diacetylenic diketones (see article [13]).
Early work by a group including one of the co-inventors of the present application (articles [9] through [11]) and others (article [12]), demonstrated that poly(enaminoesters), prepared with aromatic diamines, could be cyclized to thermally stable polyquinolones via the Conrad-Limpach reaction, as disclosed in articles [14] to [15] and represented by equation (1) as follows: ##STR1## wherein ROH is any relatively volatile aliphatic or aromatic alcohol (phenol).